Waterproofing composition and method of preparing the same



' 30 P I leather, fabric and paper without deleteriously UNITED STATES IPATENT ,oFFIcE WATERPROOFING COMIPOSI T ION AND METHOD OF PREPARING THESAME John Herman Gardthausen,

Long Island City,

N. Y., assirnor to Drlgard Products Corporation, New York, N. Y.,

aware No Drawing.

a corporation of Del- Application August 14, 1935. Se-

rial No. 36,145. Renewed July 15, 1937 34 Claims. My invention relatesto a waterproofing com- I position of matter, and more particularly to apenetrative thin liquid composition having superior waterproofingcharacteristics, and its method of manufacture.

The present application is a continuation in part of my applicationSerial No. 747,887, filed October 11,-1934. In that application, theallowed claims of which have been transferred to the presentapplication, there is disclosed a water- .proofing compositioncomprising approximately 3% aluminum stearate, 4% hydrogenated fish oil,92% light hydrocarbon distillates, e. g., xylene and Varsol (definedhereinafter) and 1% alcoholic dispersing agent selected from the loweralcohols of-the aliphatic series, e. g., ethyl alcoho]; the preferredmethod of preparation being as follows: The xylene and aluminum stearateare mixed and heated, with agitation, to about 180 F. at whichtemperature they form a heavy transparent gel or gelatinous mass. Tothis gel is added the ethyl alcohol which with agitation effects adispersion of the gel into a thin transparent colloidal mobile liquid.The hydrogenatedflsh oil in flake or granular form is then added to thethin liquid in which it readily dissolves, and finally the "Varsol" isadded. The resulting composition is substantially colorless andtransparent and may be utilized for waterproofing various materials,such as stone, brick,

. terials to be treated by any of the commonly used methods such asbrushing, spraying or immers- 'ing.

For purposes of identification of the Varsol referred to herein, some ofits published characteristics are as follows: Varsol is a volatilepetroleum distillate having a gravity of at least 45 A1 P. 11, Sayboltcolor of 22. low sulphur of about 05%, non-corrosive, and showing nocolor reaction of contacting with. sodium plumbite and sulphur. Thisdistillate, on redistilling,

should be at least 55% volatile 'at 350 F. and 95% volatile at 392 F.with a final end point of not over 410 F.

It is to be understood, however, that any other light hydrocarbonsolvent may be used in place of the above mentioned Varsol.

The present invention constitutes further de velopments along the linesof my prior applica- 5 tion, supra, and is based upon the broad, dis-.covery, resulting from numerous laboratory and 1 practical tests, thateffective waterproofing compositions possessing many desirable andvaluable characteristics may be produced in the following manner: Oneormore water insoluble soaps are properly associated with one or moresaturated or partially saturated natural of synthetical fatty acidglycerides, which are solid or semi-solid at room temperature, employinga hydrocarbon solvent or mixture of such solvents as a suspension mediumfor these associated materials, and using an alcoholic dispersing agentto reduce the composition to thin penetrative liquid form suitable forvarious applications.

The saturated or partially saturated glycerides, supra, may be thoseoccurring in natural fats, such as lard made from hog fat, tallow, andother similar natural fatty materials of a solid or nearly solidconsistency, which are composed principally of compounds of fatty acidsand glycerol. Spermaceti, which is an animal wax, may be used instead ofthe natural fat saturated glycerides. Likewise, stearin, which is one ofthe glyceride constituents of'natural fats, may 0 be used alone as thefatty material. In addition to the natural fats there is a large classof synthetic fats, produced by hydrogenation of fixed oils, that I havefound eminently suitable for combining with the other ingredientsmentioned 3'5 hereinbefore to produce my superior waterproofingcomposition. By fixed oils I mean the non-volatile oils. Similarly tothe natural fats, these fixed oils contain compounds of fatty acids andglycerol, commonly termed glycerides. their naturalform, however, theseoils are of a liquid nature, and as such are not as desirable oreifective for-use in my waterproofing composition as the solid or nearlysolid fatty substances. The oils do not dry as quickly as the syntheticor natural fats, they cannot be as easily introduced into thewaterproofing composition, and are not, per se, as efilcientwaterproofing materials as the solid fats. I It is a known inherentcharacteristic of these of saturated and partially saturated fattyacidglycerides, and it is the presence of these sub' stances and theircoaction with the other ingredients that .I believe are largelyresponsible for the superior characteristics of my composition. I havefound that in addition to the chemical differences involved, thedifierences in physical characteristics of the oils and fats account tosome extent for the superiority of the latter for producing compositionssuitable for general waterproofing purposes. These differences may beillustrated by a specific reference to menhaden fishoil and the fatproduced by its hydrogenation. If such oil, in its natural liquid form,is

combined with a water insoluble soap, e. g., aluminum stearate, ahydrocarbon solvent, and an alcoholic dispersing agent, the process forwhich is described more in detail hereinafter, the resulting compositionwill, of course, possess certain waterproofing properties, but at thesame time will possess certain undesirable characteristics. Among theundesirable characteristics is the hygroscopic nature of thecomposition. If, for example, this composition is applied to the exposedouter surface of 'a building, it will take several weeks to dry andbecome entirely effective for resisting water. It'tends to form smallemulsionlike globules with water and is, therefore, subject to beingremoved from the treated surface by heavy rains and the like- Moreover,this composition possesses a distinctly oily characteristic and theundesirable fish oil odor, both of which limit its general applications.For example, this composition would not be' suitable for waterproofingnumerous paper and fabric articles.

In contrast to the above, if the waterproofing composition is made up inthe same manner, ex-

cept that a solid or semi-solid natural fat or hydrogenated fat, such asthe fat produced by hydrogenating menhaden fish oil, is used instead 'ofthe oil, the results produced are entirely different and theabove-mentioneddisadvantages do not occur. The fat is moreeasily'handled, does not possess any undesirable odor and is practicallycolorless, so that for these reasons alone it may be used for treatingvarious materials for which the natural oil would not he satisfactory,in addition to the fact that the saturated or partially saturated fat,per se, possesses inherent substantially superior waterproofingcharacteristicsto the unsaturated oil. The fat is not hygroscopic innature and the resulting composition, instead of forming oilyglobuleadeposits in the form of a substantially colorless,

thin, tightly adherent film, which is highly water resistant. Assuggested, all of these desirable re.-

sults can be produced if a' natural or synthetical fatty material of asolid or semi-solid'nature and consisting principally of the saturatedor partially saturated fatty glycerides is used.

The improved waterproofing composition of my present invention, in allof its alternative forms,

The solid or teristics, form upon drying very brittle coatings.

These coatings are subject to fracture or complete destruction byhandling and ordinary abrasive actions. Once they are broken, of course,their waterproofing eifectiveness is lost. In view of the fact that thecomposition of my present invention does not form any thick surface Tcoating, but in contrast thereto deeply penetrates the pores of thetreated material, it is not subject to the limitations and practicaldisadvantages of the above-mentioned prior art compositions. I haveapplied the composition of my invention, in a great number of itsalternative forms, to various materials and have exposed the treatedmaterials to forced tests and excessive conditions without anysubstantial loss of. their waterproof properties.

An object of my invention is to provide a substantially transparentliquid waterproofing composition that penetrates' and tightly adheres to-the material to which it is applied without forming any noticeablecoating thereon, thatdoes not discolor the treated material and does notlose its waterproofing properties when exposed to even'unusually severeatmospheric conditions.

The composition characteristic of my invention, which, I have preparedin numerous forms and applied to various materials with satisfactoryresults, consists generically of at least one water insoluble fatty acidsoap, a solid or semi-solid fatty material consisting predominantly ofthe glycerides of saturated or'nearly saturated fatty acids, at leastone hydrocarbon solvent, and an alcoholic dispersing agent selectedpreferably natural fats, water insoluble soaps, solvents, and

dispersing agents given below.

Hydrogenated oils Hydrogenated menhaden oil Do whale oil Do sardine oilDo cod oil ,Do cod liver oil Do porgy oil Do sperm oil Do corn oil Docotton seed oil Do soya bean oil Do cocoa-nut oil Do peanut oil Doalmond oil Do rape oil Do castor oil Do .sesame oil Do olive oil Dolinseed oil Do tung oil Natural fats Lard Tallow Water insoluble soapsAluminum stearate Copper stearate Zinc stearate Calcium stearateAluminum oleate Aluminum palmitate Zinc. oleate Zinc palmitate SolventsXylene Varsol (defined hereinabove) Hydrogenated naphtha (e. g.Solvesso) defined hereinafter In preparing my waterproofing compositionin agents .its preferredforms, I have found it necessary to I use onlyone of the above-mentioned alcoholic dispersing agents and, solvents andonly one 'of either the hydrogenated oils or natural fats. It is to beunderstood, however, that whenever necessary or desirable, both thehydrogenated oils and natural fats might be used in the samecomposition, and in general that two'or more of each or all of the aboveclasses of ingredients might be used in preparing the waterproofingcomposition.

Concerning the hydrogenated oils and natural fats, I have found that formost purposes it is advantageous to use the former. Furthermore, amongthehydrogenated oils, I have found that those derived from fish andother marine animals possess of themselves superior waterproofingcharacteristics to the other oils. This does not mean, of course, thatthe natural fats and other hydrogenated oils will not worksatisfactorily, for Ihave obtained very good results using natural lardand the hydrogenated vegetable oils,

such as, for example, hydrogenated oil and hydrogenated corn oil.

Perhaps thebest results were obtained when using hydrogenated fish oils,and while I do, not wish tobe limited to any special theory in concottonseed nection with my invention, I believe that the presence of thesaturated fatty acid glycerides containing relatively high carbon andhydrogen content are largely responsible for the superior waterproofingcharacteristics of the hydrogenated fish and'marine oils. For example.in unhydrogenated whale oil,'it is my understanding that there arepresent substantial amounts of. glycerides of the highly unsaturatedfatty acids,

e, g., linoleic acid CmHazOz and clupanodonic acid CzzHssOz; and alsoglycerides of the less unsaturated or partially saturated fatty acids,such as oleic acid, C1sH34Oz; .and that in the hydrog'enated whale oil,which I use, the glycerides of the corresponding saturated fatty acidsare present insubstantial amounts, namely, the glycerides of stearicacid C1sHa6Os and glycerides of behenic acid C22H44Oz, as well asglycerides of several of 7 the hydroxy and partially saturated fattyacids.

While I am not certain that these higher saturated fatty acid glyceridesare mainly responsible for the superior properties of my composition, I

account of their green color.

have found aluminum stearate to act very efllcientiy. It is one of themost common of the waterinsoluble soaps and can be obtained economicallyin large quantities.

The solvents which are advantageously used likewise depend somewhat uponthe intended use of the final composition. The use of these hydrocarbonsolvents usually involves three problems, namely, odor, flashing point,and drying time. Where it is desired to produce a substantially odorlessliquid composition, I prefer to use one of the hydrogenated naphthas,such as the one sold under the trade name of Solvesso", which is ahydrogenated petroleum distillate having the following approximatecharacteristics: A. P. I. gravity, 34; boiling range, 275-365 F.;aniline point, 1; dimethyl sulphate value, 62;

closed flash point, 61 F. If the odor is not astioned will worksatisfactorily, I have found it advantageous to use ethyl alcohol,either in its pure or denatured form.

Although both of the classes of natural and synthetic fats worksatisfactorily, apparently due to their specific saturated fatty acidglyceride content, I prefer to use the synthetic or hydro genated fats,since they can be easily and cheaplyobtained, and although somewhatoleaginous they have sufliciently dry and pulverulent characteristics torender them easily handleable.

Three illustrative examples of the waterproofing compositioncharacteristic of my invention are given below in terms of theirrespective materials and approximate proportions.

' Example 1 I Per cent Water insoluble soap, e. g., aluminum 'stearate 6Synthetic substantially saturated fatty acid glycerides, e. g.,hydrogenated menhaden I 6 oil Hydrocarbon solvents, e. g., xylene andvarsol (defined hereinabove) 87 Aliphatiealcohol, e. g., ethyl alcohol 1m 2 Per cent Water insoluble soap, e. g., aluminum stearate "3 Syntheticsubstantially solid saturated fatty acid glycerides, e. g., hydrogenatedcotton seed oil v i 4 Hydrocarbon solvent, a g., hydrogenated naphthaAliphatic alcohol, e. g., denatured ethyl al-' cnhpl I 1 Naturalsubstantially solid saturated fatty acid glycerides, e. g., pure lardHydrocarbon solvent, e. g., hydrogenated naphtha Aliphatic alcohol, e.g., amyl alcohol 1 I believe that the waterproofing composition of myinvention, of which the above three samples are representative, is atrue composition of matter. 'I'he several ingredients comprising thiscomposition, when properly brought together, coact in such a manner thata product results having new and diiferentcharacteristics 'of its own.The waterproofing efficiency of the resultant com position is notpossessed by any one of its constituents taken individually nor is itcharacterized by a simple addition or accumulation of the individualwaterproofing ability of each of the incorporated substances.

In my co-pending application, supra, I have described in detail thecolloidal and gelatinous characteristics of aluminum stearate and theutilization of these characteristics in effecting coaction between thealuminum stearate and the hydrogenated fish oil. These characteristicsof the aluminum stearate are likewise used to advantage in the presentinvention to effect intimate association of it with the substantiallysolid saturated fatty acid glycerides. The hydrocarbon solvents areused-in the present invention to act as solvents or suspension media forthe water The alcoholic dispersing agent is used for the purposeinsoluble soap and fatty acid glycerides.

of dispersing the colloidal aluminum stearate in such a manner that theresulting composition will remain in thin liquid form over a wide rangeof temperatures, and thereby permit easy and emcient application of thecomposition to various porous materials. The combined action of thehydrocarbon solvents and the alcoholic dispersing agent effects a highlypenetrative form of solution, which is particularly advantageous in thatit causes deep impregnation of the treated materia'l and eliminates theformation of any thick surface coating thereon.

The saturated or partially saturated fatty acid glycerides, I havefound, serve the useful dual purpose of increasing the waterproofingeffectiveness of the water insoluble soaps, such as aluminum stearate,and at the same time overcome the natural tendency of these soaps tobecome dry and powdery upon long exposure, thus lengthening the usefullife of the water insoluble soap and thereby the value and effectivenessof th waterproofing composition.

When my composition is applied to any porous material, the hydrocarbonsuspension agents and the alcoholic dispersing agent evaporate fairlyrapidly'leaving on all surfaces that have been touched by thepenetrating liquid a very thin,

almost imperceptible, coating of the intimately associated waterinsoluble'soap and fatty acid glycerides. This solid residue of metallicsoap and glycerides may be purposely prepared by evaporation of theliquid constituents of the comv position, and sold in such solid form asan article of commerce. Prior to its use this solid composition isredissolved or suspended in one of the suitable solvents such as thosenamed hereinbefore.

To this hot dispersed colloidal type of solution is added a suitableamount of the substantially solid saturated fatty acid glycerides,preferably in ground or flake form. The glycerides-dissolve in the hotsolvent and coact with the colloidal aluminum stearate to form the newcomposition.

If desired, the composition may be prepared by simultaneously mixing allof the ingredients except the alcohol and heating the mixture to atemperature of approximately F'., at which point the mixture will becomesomewhat viscous. The alcohol is then added to disperse .it and form thethin penetrative type of colloidal solution.

As a result of a number of tests, which I have made in preparing mycomposition, I find that the best waterproofing results are obtainedwhen the aluminum stearat'is so treated that it forms the heavy gelmentioned above, which gel is subsequently dispersed with alcohol. Ihave also found that this gel will not be formed ,when certain petroleumdistiilates, such as varsol, are used as the initial dissolving agent,nor when certain other substances, such as the fatty .acid glycerides,are present.

This gel is easily and effectively produced, however, when, as.described above, the. aluminum stearate'is heated to the propertemperature in a coal tar distillate such as xylene.

It is to be understood that the doctrine of equivalents applies withfull force and effect to the composition of matter disclosed in thisapplication and that various modifications obvious to those skilled inthe art may be made without departing from my invention, the scope ofwhich is to be limited only by the appended claims.

What I claim as new is:

1. A liquid waterproofing composition of matter-comprising a waterinsoluble soap, a normala hydrocarbon solvent, and a dispersing agentselected from the lower aliphatic alcohols.

3. A penetrative liquid waterproofing composition of matter comprising awater insoluble soap, a synthetic normally solid fatty acid glyceride, ahydrocarbon solvent, and a dispersing agent selected from the loweraliphatic alcohols.

4. Aliquid penetrative waterproofing compo-,

sition of matter comprising a water insoluble soap, a natural fatcomposed predominantly of saturated and partially saturated glyceridesoi' the higher fatty acids, a hydrocarbon solvent, and a lower aliphaticalcohol.

5. A liquid waterproofing composition of matter comprising a waterinsolublesoap, a hydrogenated fat composed predominantly of glyceridesof the higher fatty acids. a hydrocarbon solvent, and an alcoholicdispersing agent selected from the lower alcohols of the aliphaticseries. 6. A liquid waterproofing composition of matgas ; er aliphaticalcohol.

'7. A liquid waterproofing composition of mat- I ter comprising aluminumstearate, a hydrogenated marine animal oil composed predominantly ofglycerides of the higher saturated fatty acids, ahydrocarbon solvent,and an alcoholic dispersing agent selected fromthe lower alcohols of thealiphatic series.

- 8. A liquid waterproofing composition of matter comprising a waterinsoluble soap, a hydrogenated vegetable oil composed predominantly .ofglycerides of the higher saturated fatty acids,

a hydrocarbon solvent,-and a lower aliphatic alcohol.

9. A liquid waterproofing composition of matter comprising aluminumstearate, a saturated fatty acid glyceride solid at room temperatures, ahydrocarbon solvent, and a lower aliphatic alcohol.

10. A liquid waterproofing composition of matter comprising -a waterinsoluble soap, a

fatty material substantially solid at room temperature and composedprincipally of a mixture of saturated and nearly saturated fatty acidglycerides, a hydrocarbon solvent and a lower aliphatic alcohol.

11. A liquid waterproofing composition of matter comprising aluminumstearate, a fatty bon solvent, and a lower aliphatic alcohol.

12.- The method of preparing a liquid waterproofing composition ofmatter comprising heating a metallic fatty. acid water insoluble soap ina coal tar distillate until said soap forms a heavy viscous gel-likemass, adding a relatively small .quantity of an alcoholic dispersingagent selected from the lower alcohols of the aliphatic series to effectdispersion of said gel into a fluent liquid, and adding to this heated.liquid an amount of a normally solid fattyacid glyceride, withagitation, whereby said water insoluble soap in colloidal conditionandsaid glyceride are intimately associated.

13. The method of preparing a thin liquid waterproofing composition ofmatter comprising admixing a water insoluble soap, a hydro-- carbonsolvent and a substantially saturated fatty acid glyceride, heating thismixture until it becomes 'viscous,'and adding to the viscous"hydrocarbon distillate, and a lower alcohol of the mixture a loweraliphatic alcohol to convertthe mixture into a thin fiuent liquid.

aliphatic series.

15. A waterproofing composition of matter comprising an intimateadmixture of water insoluble metallic fatty acid soap and hydrogenated-16. A waterproofing composition of matter com prising intimatelyassociated water insoluble metallic fatty acid soap, and a compatiblefatty I hydrogenated'oil adapted to coact with said water insoluble soapto form an intimate admixture therewith such that it acts to preventsaid soap from assuming its naturally non-adherent characteristics. 17.A liquid waterproofing composition of mattfcomprising a water insolublesoap, hydrogensolvent. and a lower 1 7 alcohol of the aliphatic series.Y

ated fish oil, a hydrocarbon dry. powdery and.

19. A method of preparing a liquid water-proofing composition of mattercomprising heating a mixture. of water insoluble soap and hydrocarbonsolvent until a gelatinous mass or gel is formed,

then adding thereto a relatively small quantity of a lower aliphaticalcohol to effect dispersion of said gel into a thin colloidal typeliquid, and adding thereto a hydrogenated fattyoil to coact with saidwater insoluble soap to form an intimate v admixture therewith.

20. A transparent colloidal penetrative partially evaporable liquidwaterproofing composition comprising a hydrocarbon solvent, a waterinsoluble soap, a hydrogenated fish oil and a lower aliphatic alcohol,in intimate admixture.

21. In a method of preparinga liquid watering a water insoluble soap ina hydrocarbon solvent until the mixture forms a gel orgelatinous massand subsequently adding a normally substantially solid fatty acidglyceride.

22. In a method of preparing a liquid waterproofing composition, thesteps comprising heating a water insoluble soap in a hydrocarbon solventuntil the mixture iorms a transparent gel and subsequently adding asubstantially saturated fatty acid glyceride.

23. A method of preparing a liquid waterproof ing compositioncomprisingheating a water insoluble soap and. a hydrocarbon solventuntil the mixture forms a gel, adding a lower aliphatic alcohol toconvert the gel into a thin colloidal .dispersion, and adding thereto anormally substantially solid fatty acid glyceride.

24. A liquid waterproofing composition'comprising a mobile colloidaldispersion of a water proofing composition, the steps comprisingheatprising a mobile colloidal dispersion of a metallic fatty acid soapand a hydrocarbon solvent, intimately admixed with a normallysolid-fatty acid glyceride dissolved in said solvent.

26. In a method of preparing a liquid waterproofing composition ofmatter containing a water insoluble soap, a normally solid fatty acidglyceride, a hydrocarbon solvent, and a lower alcohol of the aliphaticseries, the steps'of heating said water insoluble soap in thehydrocarbon solvent until a substantially transparent gelatinous mass isformed and then adding thereto a relatively small quantity of the loweraliphatic alcohol to effect dispersion of said mass into a thincolloidal type of liquid.

27. In a method of preparing a liquid waterproofing composition ormatter comprising heating a water insolublesoap and a, hydrocarbonsolvent until a gelatinousmass is. formed and subsequently adding anormally solid fatty acid glyceride, the step which consists of adding.a

relatively small amount of a. lower aliphatic alcohol to said gelatinousmass to effect dispersion thereof into a thin colloidal liquid. 28. Atransparent colorless liquid waterproofing composition of mattercomprising aluminum stearate, hydrogenated fish oil, a mixture of lighthydrocarbon distillates. and a lower alcohol of the aliphatic series. I4

intimate admixture with each other.

29. A transparent colorless liquidwaterproofing composition of matterconsisting of approximately 3% of aluminum stearate, 4% of hydrogenatedfish oil, 92% light hydrocarbon solvents, and 1% alcoholic dispersingagent selected from the lower alcohols of the aliphatic series.

30. A liquid composition of matter for waterproofing porous materialscomprising aluminum stearate, hydrogenated fish oil, light hydrocarbonsolvents and ethyl alcohol incorporated in such manner that uponapplication of the composition to a. porous material the liquidingredients of the composition'will cause deep penetration of thecomposition into the treated material and uponevaporation oi the liquidsthere will result a tightly adherent residue consisting of thehydrogenated fish oil and aluminum stearate in 31. A colorlesstransparent thin liquid waterproofing .composition comprising acolloidal dispersion of aluminum stearate intimately associated withhydrogenated fish oil in a liquid medium of light hydrocarbon solventsand an alcoholic dispersing agent selected from the lower alcohols ofthe aliphatic series.

32. The method of preparing a colloidal liquid waterproofing compositionof matter. comprising mixing aluminum stearate with a compatible lighthydrocarbon solvent, heating said mixture sufllciently to form asubstantially transparent viscous gel-like mass, adding a relativelysmall quantity of a lower aliphatic alcohol to this mass to causedispersion of the mass into a fluent liquid, and adding to* this hotliquid an amount of hydrogenated fishfoil with agitation, wherebythehydrogenatedflsh oil and colloidal aluminum stearate are intimatelyassociated.

33. Themethod of preparing a thin liquid colloidal composition of matterhaving waterproofing properties comprising admixing aluminum stearate,at least one light hydrocarbon distillate and hydrogenated fish oil,heating this mixture until it becomes viscous, and adding to the viscousmixture an alcoholic dispersing agent selected from the lower alcoholsof the aliphatic series to con-' -vert the mixture into a thin fluentcolloidal type of liquid. V

34. A waterproofing composition of matter comprising a mixture ofintimately associated aluminum stearate and hydrogenated fish oil.

JOIm HERMAN GARD'I'HAUSEN.

